Methods of etching insulative materials, of forming electrical devices, and of forming capacitors

ABSTRACT

In one aspect, the invention encompasses a method of etching insulative materials which comprise complexes of metal and oxygen. The insulative materials are exposed to physical etching conditions within a reaction chamber and in the presence of at least one oxygen-containing gas. In another aspect, the invention encompasses a method of forming a capacitor. An electrically conductive first layer is formed over a substrate, and a second layer is formed over the first layer. The second layer is a dielectric layer and comprises a complex of metal and oxygen. A conductive third layer is formed over the second layer. The first, second and third layers are patterned into a capacitor construction. The patterning of the second layer comprises exposing the second layer to at least one oxygen-containing gas while also exposing the second layer to physical etching conditions.

This patent resulted from a continuation application of U.S. patent application Ser. No. 09/978,489, filed Oct. 15, 2001 now U.S. Pat. No. 6,528,429 which is a continuation application of U.S. patent application Ser. No. 09/360,869 which was filed on Jul. 23, 1999, now U.S. Pat. No. 6,358,857.

TECHNICAL FIELD

The invention pertains to methods of etching insulative materials, and in particular embodiments pertains to methods of forming electrical devices, such as, for example, methods of forming capacitors.

BACKGROUND OF THE INVENTION

Semiconductor device fabrication frequently comprises removal of materials by etching. Etching methods can be divided into three general categories. A first category comprises so-called chemical etching, wherein an etchant gas chemically reacts with a material which is to be removed to convert such material to a form which can be readily removed. Another type of etching is so-called physical etching, wherein a material is bombarded with particles which displace the material. The bombarding particles are non-reactive with the material, and accordingly displace the material through purely physical interactions. Such physical etchant processes are sometimes referred to as “ion-milling”. The third category of etching comprises a combination of physical and chemical etching. An etching gas is provided which comprises some components that chemically react with the material which is to be etched to form a modified material. The gas also comprises components which are non-reactive with either the material which is to be etched or the modified material, but which displace the one or both of the material which is to be etched and the modified material through physical interactions.

It is noted that any one of the three categories of etching processes discussed above (i.e., the chemical, physical, or combined chemical/physical processes) can be conducted in the presence of plasma, and that the physical etches are typically conducted in the presence of a plasma.

In another aspect of the prior art, a number of materials have been introduced for semiconductor electronic device fabrication which are difficult to etch with anything but physical etch processes. Such materials include, for example, platinum and palladium. Platinum and palladium have been used for, for example, electrodes in capacitor constructions. Other materials utilized in capacitor constructions are dielectric materials, such as, for example, silicon dioxide, silicon nitride tantalum pentoxide, barium strontium oxide, and strontium bismuth tantalate. Dielectric materials can be, for example, chosen from the group consisting of Ba_((1-x))Sr_(x)O₃, PbZr_((1-x))Ti_(x)O₃, PZT with various dopants such as LA etc., Sr_((1-x))Bi_(x)TaO₃, Sr_((1-x))Bi_(x)TiO₃ and all of the other Smolenski compounds, PbMg_((1-x))Nb_(x)TiO₃ (PMN), compounds with PbTiO₃ (PMN-PT), CaBi₂Nb₂O₉, SrBi₂Nb₂O₉, BaBi₂Nb₂O₉, PbBi₂Nb₂O₉, BaBi₂NbTi₂O₉, BaBi₄Ti₄O₁₅, CaBi₂Ta₂O₉, SrBi₂Ta₂O₉, BaBi₂Ta₂O₉, PbBi₂Ta₂O₉, Bi₄Ti₃O₁₂, SrBi₄Ti₄O₁₅, BaBi₄Ti₄O₁₅, PbBi₄Ti₄O₁₅, (Pb, Sr)Bi₂Nb₂O₉, (Pb, Ba)Bi₂Nb₂O₉, (Ba, Ca)Bi₂Nb₂O₉, (Ba, Sr)Bi₂Nb₂O₉, BaBi₂Nb₂O₉, Ba_(0.75)Bi_(2.25)Ti_(0.25)Nb_(0.75)O₉, Ba_(0.25)Bi_(2.75)Ti_(0.25)Nb_(1.25)O₉, Ba_(0.25)Bi_(2.75)Ti_(0.75)Nb_(1.25)O₉, Bi₃TiNbO₉, SrBi₂Nb₂O₉, Sr_(0.8)Bi_(2.2)Ti_(0.2)Nb_(1.8)O₉, Sr_(0.6)Bi_(2.4)Ti_(0.4)Nb_(1.6)O₉, Bi₃TiNbO₉, PbBi₂Nb₂O₉, Pb_(0.75), Bi_(2.25)Ti_(0.25)Nb_(1.75)O₉, Pb_(0.5)Bi_(2.5)Ti_(0.5)Nb_(1.5)O₉, Pb_(0.25)Bi_(2.75)Ti_(0.75)Nb_(1.25)O₉, Bi₃TiNbO₉, PbBi₄Ti₄O₁₅, Pb_(0.75)Bi_(4.25)Ti_(3.75)Ga_(0.25)O₁₅, Pb_(0.5)Bi_(4.5)Ti_(3.5)Ga_(0.5)O_(1.5), and Bi₅Ti₃GaO₁₅.

Several of the dielectric materials being utilized for capacitor constructions, or being proposed for utilization in capacitor constructions, correspond to complexes of metal and oxygen, such as, for example, tantalum pentoxide, barium strontium oxide, etc. Such complexes can have advantages over more traditional materials, such as, for example, silicon dioxide or silicon nitride, in that the complexes of metal and oxygen can comprise higher dielectric constants than the traditional complexes.

Problems are occasionally encountered during etching of materials, such as, for example, during etching of metal and oxygen complexes. Accordingly, it would be desirable to develop new etching methods for utilization in semiconductor device fabrication.

SUMMARY OF THE INVENTION

In one aspect, the invention encompasses a method of etching insulative materials which comprise complexes of metal and oxygen. The insulative materials are exposed to physical etching conditions within a reaction chamber and in the presence of at least one oxygen-containing gas.

In another aspect, the invention encompasses a method of forming a capacitor. An electrically conductive first layer is formed over a substrate, and a second layer is formed over the first layer. The second layer is a dielectric layer and comprises a complex of metal and oxygen. A conductive third layer is formed over the second layer. The first, second and third layers are patterned into a capacitor construction. The patterning of the second layer comprises exposing the second layer to at least one oxygen-containing gas while also exposing the second layer to physical etching conditions.

BRIEF DESCRIPTION OF THE DRAWINGS

Preferred embodiments of the invention are described below with reference to the following accompanying drawings.

FIG. 1 is a diagrammatic, cross-sectional, fragmentary view of a semiconductor wafer fragment shown at an initial processing step of a capacitor-forming method of the present invention.

FIG. 2 is a view of the FIG. 1 wafer fragment shown at a processing step subsequent to that of FIG. 1.

FIG. 3 is a view of the FIG. 1 wafer fragment shown at a processing step subsequent to that of FIG. 2.

FIG. 4 is a view of the FIG. 1 wafer fragment shown at a processing step subsequent to that of FIG. 3.

FIG. 5 is a view of the FIG. 1 wafer fragment shown at a processing step subsequent to that of FIG. 4.

FIG. 6 is a view of the FIG. 1 wafer fragment shown at a processing step subsequent to that of FIG. 5.

FIG. 7 is a diagrammatic, fragmentary, cross-sectional view of a semiconductor wafer fragment at a preliminary step of a second embodiment capacitor fabrication process encompassed by the present invention.

FIG. 8 is a view of the FIG. 7 wafer fragment shown at a processing step subsequent to that of FIG. 7.

FIG. 9 is a diagrammatic, fragmentary, cross-sectional view of a semiconductor wafer fragment shown at an initial step of a third embodiment capacitor-forming process encompassed by the present invention.

FIG. 10 is a view of the FIG. 9 wafer fragment shown at a processing step subsequent to that of FIG. 9.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

This disclosure of the invention is submitted in furtherance of the constitutional purposes of the U.S. Patent Laws “to promote the progress of science and useful arts” (Article 1, Section 8).

A first embodiment method encompassed by the present invention is described with reference to FIGS. 1-7 as a method for forming a capacitor construction. Referring initially to FIG. 1, a semiconductor wafer fragment 10 is illustrated at a preliminary step of the method. Wafer fragment 10 comprises a substrate 12. Substrate 12 can comprise, for example, a semiconductive material, such as monocrystalline silicon. Such semiconductive material can be lightly doped with a conductivity-enhancing dopant. To aid in interpretation of the claims that follow, the terms “semiconductive substrate” and “semiconductor substrate” are defined to mean any construction comprising semiconductive material, including, but not limited to, bulk semiconductive materials such as a semiconductive wafer (either alone or in assemblies comprising other materials thereon), and semiconductive material layers (either alone or in assemblies comprising other materials). The term “substrate” refers to any supporting structure, including, but not limited to, the semiconductive substrates described above.

An insulative material 14 is formed over substrate 12. Insulative material 14 can comprise, for example, borophosphosilicate glass (BPSG), and can be formed by, for example, chemical vapor deposition. An electrical node 16 is formed within substrate 12, and in the shown embodiment comprises a conductively-doped diffusion region. An opening 18 extends through insulative material 14 to node 16, and a conductive material 20 is formed within opening 18. Conductive material 20 can comprise, for example, an elemental metal, a metal alloy, and/or conductively doped polysilicon.

A conductive material 22 is formed over insulative material 14, and in electrical connection with material 20. Material 20 thus defines an electrical connection between conductive material 22 and node location 16. Conductive material 22 is ultimately to be patterned into a storage node for a capacitor construction and can comprise, for example, platinum or palladium. Among the materials suitable for conductive material 22 are: TiPt, TiNPt, TiAlN-Pt, Ru, RuO₂, RuPt, RuO₂Pt, W, WPt, WSi, Ti, TiSi, Ta, TaN, TaSi, doped and undoped Poly Si, Al, Pd and Ir.

A masking material 24 is provided over conductive material 22. Masking material 24 can comprise, for example, photoresist. Masking material 24 is shown in the configuration of a patterned block, and can be formed into such configuration by, for example, photolithographic processing of photoresist with a patterned beam of light.

Referring to FIG. 2, fragment 10 is shown after material 22 has been exposed to etching conditions. Such etching conditions can vary depending on the chemical composition of material 22. The etching can, for example, comprise a physical etch. An exemplary physical etch utilizes argon to bombard and displace portions of material 22 which are not protected by masking material 24. The etching of material 22 patterns such material into a first capacitor electrode 26.

Referring to FIG. 3, masking layer 24 is removed and a dielectric material 28 is formed over storage node 26. Dielectric material 28 can comprise, for example, a complex comprising metal and oxygen. Exemplary dielectric materials comprising metal and oxygen are described in the “Background” section of the this disclosure, and include tantalum pentoxide and barium strontium oxide. Alternatively, material 28 can comprise silicon dioxide or silicon nitride.

A second patterned masking material 30 is formed over dielectric material 28 and utilized to mask a portion of material 28 during a subsequent etch.

FIG. 4 shows fragment 10 after material 28 has been subjected to an etch. Such etch can be a physical etch, and in preferred embodiments consists essentially of a physical etch. After the etch, vertically extending portions 32 of material 28 are along sidewalls of storage node 26, and a horizontally extending portion 34 of material 28 is beneath masking material 30.

Exemplary etch conditions utilize an Ion Beam Etch System reaction chamber, obtained from VEECO of Milpitas, Calif., with an argon-containing plasma, a power of 900 volts, a current of 368 milliamps, and an angle of the wafer to an anode of about 50°.

At least one oxygen-containing gas is flowed through the reaction chamber during the physical etching of material 28. Such oxygen-containing gas can, for example, be selected from the group consisting of O₃, O₂, H₂O₂, and mixtures thereof.

It is found that inclusion of the oxygen-containing gas during the physical etching can improve insulative properties of an etched dielectric layer relative to the properties of a layer etched under similar physical etching conditions, but without the inclusion of the oxygen-containing gas. A possible mechanism by which the oxygen-containing gas can improve properties of physically etched oxygen-containing dielectric materials is that the oxygen-containing gas replaces oxygen displaced from the oxygen-containing dielectric materials by the physical etching conditions. This mechanism could be particularly germane in situations wherein dielectric materials comprising complexes of metal and oxygen are physically etched. If a physical etch process displaces oxygen from a complex of metal and oxygen, then it will effectively leave metal behind. Such metal can be a conductive material and lessen the dielectric properties of the etched metal/oxygen complex. However, if the displaced oxygen is replaced by oxygen from an oxygen-containing gas, the conductive metal can be converted back to an insulative metal/oxygen material.

It is to be understood that the mechanism presented above is provided merely to assist persons in understanding aspects of the present invention, and is not intended to limit the claims which follow. Further, it is to be understood that although the mechanism is discussed with reference to improvement of properties pertaining to metal/oxygen complexes, the invention encompasses embodiments wherein oxygen is flowed into physical etch processes which are utilized for etching materials other than metal/oxygen complexes. Such other materials can comprise, for example, silicon nitride and silicon dioxide.

After the physical etching of material 28 has been stopped, material 28 can be exposed to an additional oxygen treatment to further replace oxygen which may have been lost during the physical etching. Such oxygen treatment can comprise, for example, exposing the etched insulative material 28 to at least one oxygen-containing gas selected from the group consisting of O₃, O₂, H₂O₂, and mixtures thereof, at a temperature of at least about 750° C. A difficulty with such processing is that it can melt particular conductive materials which may be utilized for interconnect 20 or first electrode 26. Accordingly, the exposure of material 28 to temperatures of at least about 750° C. is preferably conducted only when interconnect 20 and electrode 26 are formed of materials which can withstand such high temperature processing.

Referring to FIG. 5, masking material 30 is removed and a second conductive material 40 is provided over dielectric material 28. Second conductive material 40 is physically separated from first conductive material 22 by dielectric material 28, and can comprise, for example, conductively doped polysilicon or a metal selected from the group consisting of Ti, Pd, Pt and W. Among the materials suitable for conductive material 40 are: TiPt, TiNPt, TiAIN-Pt, Ru, RuO₂, RuPt, RuO₂Pt, W, WPt, WSi, Ti, TiSi, Ta, TaN, TaSi, doped and undoped Poly Si, Al, Pd and Ir.

A patterned masking material 42 is formed over conductive material 40. Subsequently, material 40 is etched to form a second capacitor electrode 44 as shown in FIG. 6. The etching of material 40 can be accomplished by, for example, a physical etch. First capacitor electrode 26, dielectric material 28 and second capacitor electrode 40 together comprise a capacitor assembly 50.

In subsequent processing (not shown) masking material 42 can be removed and capacitor construction 50 can be electrically connected with other circuitry to form, for example, a dynamic random access memory (DRAM) device.

The processing described above with reference to FIGS. 1-6 is but one embodiment of forming a capacitor construction in accordance with the present invention. Another embodiment method of forming a capacitor construction is described with reference to FIGS. 7 and 8. In referring to FIGS. 7 and 8, similar numbering will be used as was utilized above in describing the embodiment of FIGS. 1-6, with the suffix “a” used to identify structures shown in FIGS. 7 and 8.

Referring to FIG. 7, a semiconductor wafer fragment 10 a comprises a substrate 12 a having an insulative material 14 a formed thereover. An electrical node 16 a is provided within substrate 12 a, and a conductive material 20 a extends through insulative material 14 a to connect with electrical node 16 a. A first conductive material 22 a is formed over insulative material 14 a, and subsequently a dielectric material 28 a and a second conductive material 40 a are formed over first conductive material 22 a. Materials 12 a, 14 a, 20 a, 22 a, 28 a and 40 a can comprise identical materials as those discussed above with reference to FIGS. 1-6 for materials 12, 14, 20, 22, 28 and 40, respectively. A patterned masking material 30 a is provided over conductive material 40 a.

Referring to FIG. 8, materials 22 a, 28 a and 40 a are subjected to an etch. The etch patterns materials 22 a, 28 a and 40 a into a capacitor construction 50 a comprising a first capacitor electrode 26 a, dielectric material 28 a, and a second capacitor electrode 44 a.

The etching utilized to pattern materials 22 a, 28 a and 40 a preferably comprises a physical etch and consist essentially of a physical etch. Preferably, an oxygen-containing gas is flowed through a reaction chamber comprising fragment 10 a during the physical etching of materials 26 a, 28 a and 44 a. Such oxygen-containing gas can comprise, for example, a gas selected from the group consisting of O₃, O₂, H₂O₂, and mixtures thereof.

After the physical etching conditions utilized to etch materials 26 a, 28 a and 44 a are ceased, dielectric material 28 a can be further treated with an additional oxygen treatment. Such oxygen treatment can comprise, for example, exposing material 28 a to an oxygen-containing gas selected from the group consisting of O₃, O₂, H₂O₂, and mixtures thereof, and to a temperature of at least about 750° C. A difficulty with such processing is that it can melt particular conductive materials which may be utilized for interconnect 20 a, first electrode 26 a, or second electrode 44 a. Accordingly, the exposure of material 28 a to temperatures of at least about 750° C. is preferably conducted only when interconnect 20 a and electrodes 26 a and 44 a are formed of materials which can withstand such high temperature processing.

A difficulty in using physical etching to etch through all of materials 40 a, 28 a and 22 a can result from having material 22 a etched after dielectric material 28 a. Specifically, conductive fragments displaced by the etching of material 22 a can wrap along exposed surfaces of dielectric material 28 a and cause a short between materials 22 a and 40 a. Accordingly, it can be desirable to etch material 22 a separately from material 28 a. The embodiment of FIGS. 1-6 is one method of accomplishing such separate etching. Another method is described with reference to FIGS. 9 and 10. In referring to FIGS. 9 and 10, similar numbering will be utilized as was used above in describing the embodiment of FIGS. 1-6, with the suffix “b” used to indicate structures shown in FIGS. 9 and 10.

Referring to FIG. 9, a semiconductor wafer fragment 10 b is shown at a processing step subsequent to that of FIG. 2. Specifically, the wafer fragment of FIG. 9 comprises a conductive material 22 b which has been patterned into a first capacitor electrode 26 b. After such patterning, a dielectric material 28 b is provided over capacitor electrode 26 b, and a conductive material 40 b is provided over dielectric material 28 b. A masking material 30 b is provided over conductive material 40 b, and utilized to pattern materials 28 b and 40 b into the capacitor construction 50 b shown in FIG. 10. The patterning of materials 28 b and 40 b is preferably accomplished with a physical etch in a reaction chamber having an oxygen-containing gas flowing therethrough. The etch converts material 40 b into a second capacitor electrode 44 b which is separated from first capacitor electrode 26 b by dielectric material 28 b.

Although methods of the present invention are described above with reference to applications for forming capacitor structures, it is to be understood that the invention can be utilized in other aspects of semiconductor processing. Such other aspects include, for example, etching of dielectric materials for forming insulative caps over wordlines, and etching of dielectric materials for forming insulative structures between electronic devices.

In compliance with the statute, the invention has been described in language more or less specific as to structural and methodical features. It is to be understood, however, that the invention is not limited to the specific features shown and described, since the means herein disclosed comprise preferred forms of putting the invention into effect. The invention is, therefore, claimed in any of its forms or modifications within the proper scope of the appended claims appropriately interpreted in accordance with the doctrine of equivalents. 

What is claimed is:
 1. A semiconductor processing method comprising: providing a substrate comprising an insulative material within a reactor; flowing a gas comprising at least one of H₂O₂ and O₃ through the reactor; and while flowing the gas, performing a physical etch of the insulative material, at least some oxygen from the gas being incorporated into the insulative material during the etching.
 2. The method of claim 1 wherein the gas additionally comprises O₂.
 3. The method of claim 1 wherein the insulative material comprises at least one member selected from the group consisting of Ba_((1-x))Sr_(x)O₃, PbZr_((1-x))Ti_(x)O₃, PZT, Sr_((1-x))Bi_(x)TiO₃, PbMg_((1-x))Nb_(x)TiO₃, PbTiO₃, CaBi₂Nb₂O₉, SrBi₂Nb₂O₉, BaBi₂Nb₂O₉, PbBi₂Nb₂O₉, BiBi₂NbTiO₉, BaBi₄Ti₄O₁₅, CaBi₂Ta₂O₉, BaBi₂Ta₂O₉, PbBi₂Ta₂O₉, Bi₄Ti₃O₁₂, SrBi₄Ti₄O₁₅, BaBi₄Ti₄O₁₅, PbBi₄Ti₄O₁₅, (Pb, Sr)Bi₂Nb₂O₉, (Pb, Ba)Bi₂Nb₂O₉, (Ba, Ca)Bi₂Nb₂O₉, (Ba, Sr)Bi₂Nb₂O₉, BaBi₂Nb₂O₉, Ba_(0.75)Bi_(2.25)Ti_(0.25)Nb_(1.75)O₉, Ba_(0.25)Bi_(2.75)Ti_(0.75)Nb_(1.25)O₉, Ba_(0.25)Bi_(2.75)Ti_(0.75)Nb_(1.25)O₉, Bi₃TiNbO₉, SrBi₂Nb₂O₉, Sr_(0.8)Bi_(2.2)Ti_(0.2)Nb_(1.8)O₉, Sr_(0.6)Bi_(2.4)Ti_(0.4)Nb_(1.6)O₉, Bi₃TiNbO₉, PbBi₂Nb₂O₉, Bi_(2.25)Ti_(0.25)Nb_(1.75)O₉, Pb_(0.5)Bi_(2.5)Ti_(0.5)Nb_(1.5)O₉, Pb_(0.25)Bi_(2.75)Ti_(0.75)Nb_(1.25)O₉, Bi₃TiNbO₉, PbBi₄Ti₄O₁₅, Pb_(0.75)Bi_(4.25)Ti_(3.75)Ga_(0.25)O₁₅, Pb_(0.75)Bi_(4.25)Ti_(3.75)Ga_(0.5)O_(1.5), and Bi₅Ti₃GaO₁₅.
 4. The method of claim 1 wherein the insulative material is disposed over a patterned conductive material.
 5. The method of claim 4 wherein the conductive material is selected form the group consisting of TiPt, TiAIN-Pt, Ru, RuO₂, RuPt, W, WPt, WSi, Ti, TiSi, Ta, TaN, TaSi, polysilicon, conductively doped polysilicon, Al, Pd and Ir.
 6. The method of claim 1 further comprising: ceasing the physical etching; and after ceasing the physical etching, exposing the insulative material to a temperature of at least 750° C. in the presence of an oxygen-containing gas selected from the group consisting of O₂, H₂O₂, O₃, and mixtures thereof.
 7. A method of forming a capacitor, comprising: forming an electrically conductive first layer; forming a second layer comprising an insulative material over the first layer; forming a conductive third layer over the second layer; and patterning the first, second and third layers into a capacitor construction, the patterning the second layer comprising physically etching the insulative material in a reaction chamber while flowing a gas through the reaction chamber, the gas comprising at least one of O₃ and H₂O₂, at least some oxygen from the gas being incorporated into the insulative material during the physically etching.
 8. The method of claim 7 wherein the third layer comprises at least one of Pd and Pt.
 9. The method of claim 7 wherein the insulative material comprises tantalum pentoxide.
 10. The method of claim 7 wherein the gas additionally comprises O₂.
 11. The method of claim 7 wherein the patterning the first layer occurs prior to the forming the second layer.
 12. The method of claim 4 wherein the conductive material comprises at least one of N, Ti, Si, Pt, W, Ta, Ru, Al, Pd and Ir. 